Minerals Engineering 171 (2021) 107119

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Combined treatment based on synergism between hydrodynamic cavitation

and H2O2 for degradation of cyanide in effluents
Javier P. Montalvo Andia a, Alberth E. Ticona Cayte b, Jocelyn M. Illachura Rodriguez b,
Lizandra López Belón a, Miguel A. Cárdenas Málaga b, Luiz Alberto Cesar Teixeira c, *
a
Escuela de Ingeniería Ambiental, Universidad Católica San Pablo, Arequipa, Peru
b
Escuela de Ingeniería Química, Universidad Nacional de San Agustín, Arequipa, Peru
c
Pontificia Universidade Católica do Rio de Janeiro, Department of Chemical and Materials Engineering, Rio de Janeiro, Brazil and Peroxidos do Brasil Ltda. (Solvay
Group), Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: The main purpose of this research has been to evaluate and optimize the application of hydrodynamic cavitation
Cyanide removal (HC), combined with hydrogen peroxide, as a promising process for the effective degradation of cyanide in
Hydrodynamic cavitation aqueous effluents. The experimental work was carried out using cavitation equipment with a venturi device
Hybrid treatment
connected to a tubular circuit which allowed a closed-cycle flow to run for 120 min, in which the effect of control
Slit venturi
Kinetic study
parameters as inlet pressure, H2O2:CN─ ratio, pH, and temperature have been evaluated for the treatment of
Operational cost solutions with initial cyanide concentration in range 100 to 550 mg L─1.
The results showed that in optimal conditions cyanide degradation using only HC reached 70% and, using
solely H2O2 as oxidizing agent it reached 63%. Efficiency of the combined treatment process was evaluated on
the basis of their synergetic effect as it turned out to be more effective showing a 99.9 % cyanide degradation in
less than 120 min. The optimum set of conditions that produced the highest degradation rate and efficiency was:
inlet pressure 4 bar; pH 9.5; and H2O2:CN─ ratio = 1.5:1. The process was also evaluated on the basis of cav­
itational yield and in terms of energy and chemical treatment costs. The results have demonstrated that the
combined treatment technology of HC + H2O2 can be effectively used as a fast and highly efficient treatment of
wastewater containing cyanide.

1. Introduction maximum of 1 mg L− 1 for total cyanide, and 0.022 mg L− 1 as free cya­

Cyanide solutions are employed in almost all precious metals (Au,
Ag) extraction plants worldwide (Akcil, 2003; Brüger et al., 2018;
Gurbuz et al., 2009). This usually results in the generation of large
flowrates of discharges to be dumped in tailings ponds and rivers in
rainy seasons. In such solutions, free cyanide (CN─) stands out as the
main toxic substance with concentrations typically ranging from 10 to
300 mg L− 1 (Guamán Guadalima and Nieto Monteros, 2018). Consid­
ering its toxic nature, the cautious management of cyanide species has
always been considered an issue of environmental relevance. Therefore,
remediation and treatment of such liquid effluents are mandatory before
they are released into the environment. As a reference, the maximum
concentration limit for total cyanide established by the USEPA (US
Environmental Protection Agency) in wastewaters is 0.2 mg L− 1, while
for the MINAM (Secretary of Mining and Environment) of Peru a
nide, are established for wastewater discharges into recipient bodies,
rivers in most cases.
Natural attenuation reactions and/or physical–chemical treatment
processes using, for example: hydrogen peroxide; SO2 plus air; Caro’s
Acid; alkaline chlorination; and iron / copper precipitation, can convert
cyanide to less harmful forms, decreasing its reactivity and lowering its
toxicological characteristic (Dash et al., 2009; Kim et al., 2003; Kuyucak
and Akcil, 2013; Parga et al., 2003; Teixeira et al., 2013) so treated ef­
fluents can be disposed in the environment. Although natural degrada­
tion bears low operating costs, it is a slow and efficiency-limited process
that depends largely on climatic conditions, so only partially useful. The
chemical processes are much faster and more efficient but carry much
higher costs with chemical reagents, energy and maintenance. Thus,
there is still room for improvements in the cyanide-detoxification pro­
cesses; searching for novel treatments that remove cyanide faster and

* Corresponding author.
E-mail addresses: jpmontalvo@ucsp.edu.pe (J.P. Montalvo Andia), teixeira@puc-rio.br (L.A.C. Teixeira).

https://doi.org/10.1016/j.mineng.2021.107119
Received 9 September 2020; Received in revised form 1 August 2021; Accepted 2 August 2021
Available online 14 August 2021
0892-6875/© 2021 Elsevier Ltd. All rights reserved.
J.P. Montalvo Andia et al. Minerals Engineering 171 (2021) 107119

more efficiently, with lower consumption of energy and chemicals, in 2. Materials and methods
comparison to the existing technologies.
Hydrodynamic cavitation (HC) is a promising method that works by 2.1. Chemical reagents
triggering nucleation, growth and violent collapse of microbubbles at
small time intervals with large amounts of energy released over a very Sodium cyanide and hydrogen peroxide (35 % w/w) AR grade were
small area. This produces, simultaneously, high intensity turbulences obtained from Delta Química Pvt. Ltd., Peru. The chemicals required for
and local microcirculation in small areas of the reactor due to pressure cyanide analysis by titrimetric method such as silver nitrate, p-dime­
drops below the vapor pressure of the liquid. These turbulences and thylaminobenzalrodanine (indicator) and acetone AR grade were pur­
microcirculation create “hot zones”, with temperatures ranging from chased from Diproquim Pvt. Ltd., Peru. H2SO4 (1 M) and NaOH (1 M)
extraordinary 1000–10000 K and local pressures above 1000 atmo­ were used for adjusting the pH, and deionized water was used for the
spheres depending on the proximity to the implosion zone (Choi et al., required dilutions. All chemicals were used as received from suppliers.
2020, 2019; Rajoriya et al., 2016; Sun et al., 2020) which favour the
generation of free radicals (e.g. ●OH, ●H), under controlled conditions,
2.2. Experimental set up and procedures
through thermal pyrolysis (Abbasi and Razzaghi, 2008; Song and Li,
2009; Yusof et al., 2016). Hydrodynamic cavitation could be considered
The schematic diagram of the hydrodynamic cavitation equipment is
one of the most cost-effective technologies to generate free radicals
shown in Fig. 1a. The experimental configuration entails a closed piping
(Gągol et al., 2018). It uses mechanical constraints as devices to induce
circuit; a main line, including a 20 L capacity holding tank connected to
cavitation through abrupt changes of section and changes in local
the suction end of a 1.9 HP centrifugal electric pump; flow control valves
pressure in the duct’s throat and downstream (Gogate, 2002).
(V1-V5); a slit venturi tube as cavitation reactor (shown in Fig. 1b with its
Few studies on cavitation applied to cyanide degradation have been
geometric measurements detailed in Table 1); pressure gauges (P1, P2)
found, and most of these focused on sonochemical reactors and photo­
to measure the inlet and outlet pressure of the slit venturi tube; and an
catalysis. Bonyadi et al. (Bonyadi et al., 2012) studied the efficacy of
in-line flow sensor. In addition, the tank is connected to a second bypass
cyanide removal with sonochemical reactors to induce cavitation and
line in order to control the flow and pressure of the fluid. Kinetic runs
reported a removal of 74%. Jawale and Gogate (Jawale et al., 2014)
were made with 10 L prepared samples of NaCN synthetic effluent with
reported the degradation degree of potassium ferrocyanide (K4Fe(CN)6)
initial [CN─] set in range 100 to 550 mg L− 1 and adjusted initial pH in
in solution after applying two types of cavitation methods. They found
values 9.5, 10, 10.5 and 11. The operating temperature was kept at a
that hydrodynamic cavitation was better (degradation of 44%) than
constant value ± 2 ◦ C in range 20 to 50 ◦ C, by circulating water through
acoustic cavitation. It has also been shown that the cavitation process
the jacket of the tank. Treatment time for all experiments was 120 min.
can be made more effective when combined with other AOPs or oxida­
Inlet pressure ranged from 3 to 6 bar to find the optimal pressure for CN─
tion reagents, resulting in intensification of the generation of highly
degradation. Additionally, the combination of HC and H2O2 was tried at
reactive free radicals capable of chemical oxidation, compared to stan­
different molar ratios H2O2: CN─ (1:1, 1.5:1, 3:1, 5:1, 7:1) to evaluate
dard direct oxidation process applied separately. According to Jawale
the synergy effect of this combination. All experiments were performed
and Gogate (Jawale and Gogate, 2019), the application of different
hybrid treatment approaches based on hydrodynamic cavitation and
Table 1
individual chemical oxidation approaches, resulted in an almost com­
Geometric details of slit venturi.
plete degradation of SCN─ for the combined form HC/H2O2/O3/CuO,
establishing itself as the approach that provides the greatest synergism Dimension Slit venturi

for the removal of this cyanide derivative in aqueous solution. W = 6.0 mm

Thus, in the presented context, the aim of the present research was to Throat Dimension H = 1.9 mm
L = 1.9 mm
study the kinetics and thermodynamics, searching for optimal parame­
Length of venturi 95.9 mm
ters, for the degradation of free cyanide in aqueous solutions through Length of divergent section 74 mm
hydrodynamic cavitation, and to evaluate its effectiveness when com­ Median angle of converging section 23.5◦
bined with oxidation by hydrogen peroxide. Median angle of divergent section 6.5◦

Fig. 1. (a) HC system (b) Venturi design.

2
J.P. Montalvo Andia et al.
in triplicate and the average results are reported.
2.3. Analytical methods
Free cyanide was analysed using the titrimetric method described in
Standard Methods (APHA-AWWA-WEF, 1998) using a standardized
solution of silver nitrate (0.02 M) and p-dimethylaminobenzaldanine at
0.02% w/w in acetone as an indicator. The pH and temperature values of
the solutions were measured using a multiparameter meter; model HI
98194 by Hanna Instruments.
2.4. Kinetic runs
Similarly to previous studies on the breakdown of pollutants by HC,
the rate constants for cyanide oxidation promoted by HC in the present
work were determined using the pseudo-first order kinetic model with
respect to cyanide concentration, under the reasonable assumption that
the concentration of HC-generated ●OH radicals remained constant
during the reaction. Cyanide is oxidized to cyanate following Eq. (1),
and the kinetics of the cyanide oxidation that describes an HC run is
expressed according to Eq. (2):
CN− + 2∙ OH→ CNO− + H2 O (1)
(
[CN− − ]0
) The inlet pressure is also related to the cavitation number Cv, a
ln = k.t (2)
[CN− − ]t
Where [CN–]0 and [CN–]t are the cyanide concentrations (mg L− 1) at the
beginning and at time t, respectively, and k (min − 1) is the pseudo-first
order rate constant.
3. Results and discussion
A mechanistic investigation was beyond the scope of the present
work. Nevertheless, the effects of variables which can be controlled in an
eventual industrial operation such as inlet pressure, pH, temperature
and ratio of H2O2:CN─, on a representative range of initial CN─ con­
centration, are evaluated and discussed in the light of the findings of
previous works on this field.
3.1. Effect of inlet pressure on cavitation number and reaction rate
Inlet pressure and cavitation number are two important parameters
which affect the number of cavities being generated and their collapse
intensity (Saharan et al., 2013). To study the influence of inlet pressure,
experimental runs were performed at fixed conditions of initial con­
centration of free cyanide (100 mg L− 1), pH = 11, and temperature (30
◦
C). In each experiment, pressure was set at a fixed value: 3, 4, 5 and 6
bar.
The results obtained can be seen in Fig. 2 and Table 2. A maximum
CN─ removal rate is obtained at inlet pressure = 4 bar, leading to a
maximum degradation of 51.3% in 120 min, with a first-order rate
constant of 6.49 × 10− 3 min− 1 (R2: 0.984). This same behaviour has
been reported in other studies: degradation of sodium ferrocyanide in
wastewater (Jawale et al., 2014); degradation of the pesticide tri­
azophos (Gogate and Patil, 2015); decomposition of rhodamine B (Yi
et al., 2018); degradation of textile dyes (Rajoriya et al., 2018); and
treatment of carbamazepine (Thanekar et al., 2018).
According to these previous studies, as the inlet pressure is increased
from 3 to 4 bar, the intensity of cavity collapse increases, resulting in
more extensive cyanide degradation. When cavities or microbubbles are
formed, they behave independently, collapsing immediately at the
outlet of the venturi throat; but when the pressure is further increased to
a value greater than the optimum, a larger number of cavities are
formed, combining with each other to form a large cloud (choked
cavitation) that causes microbubble implosion thus reducing free-
3
Minerals Engineering 171 (2021) 107119
Fig. 2. Effect of inlet pressure (a) on the extent of cyanide degradation, (b)
kinetic study obtained using pseudo-first order model (Hold values: [CN─]0 =
100 mg L− 1, pH = 11 and T = 30 ◦ C).
radical formation and decreasing the extent of degradation (Gągol
et al., 2018; Jawale et al., 2014; Saharan et al., 2013).
dimensionless parameter used to evaluate the cavitational intensity
which is defined by Eq. (3) (Li et al., 2019).
p2 − pv
Cv = (3)
1
2
ρv2
Where p2 represents the outlet pressure of the cavitator, pv, is the vapor
pressure of the liquid, ρ is fluid density and v, is the fluid velocity at the
venturi throat.
When the inlet pressure increases, the velocity and the mass flow of
the fluid circulating through the venturi contraction increase, the cavi­
tation number decreases according to Eq. (3). A small cavitation number
implies that a large quantity of cavities are formed producing a choked
cavitation thereby decreasing the collapse intensity (Gągol et al., 2018).
Table 2 shows how the cavitation number drops with the pressure
increase while the fluid flow increases with pressure. Capocelli et al
(Capocelli et al., 2014) also reported a fall of the cavitation number with
the increase in pressure and an increase of the fluid flow with the in­
crease of the inlet pressure in their theoretical and experimental study of
p-nitrophenol degradation by hydrocavitation. Rajoriya et al (Rajoriya
et al., 2017) also reported the same behaviour of the cavitation number
when increasing the pressure from 3 to 11 bar in the degradation of
textile dyes using slit and circular Venturi tubes.
It is generally accepted that cavities are formed under ideal condi­
tions (Cv ≤ 1) but in certain cases cavitation can start at values of Cv > 1
due to the dissolved gases or solid particles (Gągol et al., 2018; Saharan
et al., 2013). Saharan et al (Saharan et al., 2013) observed Cv values >
1.5 for low pressures and for higher pressures Cv values decreased in
circular and slit venturis. In the present study Cv values (Table 2)
decrease from 1.2 to 0.57 when increasing pressure from 3 to 5 bar,
being the optimal cavitation number of 0.88 when the highest cyanide
degradation was reached with a pressure of 4 bar.
3.2. Effect of initial cyanide concentration
The effect of initial cyanide concentration (100, 250, 400 and 550
mg L− 1) on the reaction rate and efficiency was studied at an inlet
pressure of 4 bar, pH 11 and a temperature of 30 ◦ C. Results displayed as
kinetic curves are shown in Fig. 3 and corresponding rate constants in
Table 3. A negative effect of the initial [CN─] is observed. Such behav­
iour has been consistently observed in other studies of hydrodynamic
cavitation for the oxidative degradation of various target-pollutants
J.P. Montalvo Andia et al. Minerals Engineering 171 (2021) 107119

Table 2
Cavitation numbers and first order rate constants at different inlet pressures.
Inlet pressure (bar) Volumetric flow (L h− 1) Cv Degradation in 120 min (%) Number of passes mg per pass k x103 (min− 1) R2

3 568 1.21 43.5 114 3.83 5.05 0.993

4 664 0.88 51.3 133 3.86 6.49 0.984
5 752 0.69 36.7 150 2.44 4.12 0.989
6 824 0.57 34.4 165 2.09 3.81 0.988

mg L− 1 to 550 mg L− 1.
This behavior is not consistent with true first-order kinetics, and
appears to be characteristic of HC processes, as observed by Yao et al.
(Yao et al., 2010) and Cui et al. (Cui et al., 2017).
A large concentration of the reactant CN─, saturation of the micro­
bubble interfacial region may occur hindering the diffusion of reaction
participants, including the supply of ●OH that is generated within the
cavity at constant rate, and this may result in a slowdown effect in the
degradation rate and reduced degradation efficiency. This type of het­
erogeneous gas–liquid reaction is seen to be often described by a
Langmuir-Hinshelwood model, as also been used by previous in­
vestigators of HC oxidation reactions (Gągol et al., 2018; Yao et al.,
2010).
Assuming the reaction between pollutant and free radicals is very
fast, Sivakumar et al. (Sivakumar et al., 2002) reported that at lower
initial concentration, the rate limiting step was the diffusion of pollutant
into the interfacial region (reaction zone), and the driving force would
be (Cb – CI) where Cb is the pollutant bulk concentration and CI pollutant
Fig. 3. Effect of initial cyanide concentration (a) on the extent of cyanide interfacial region concentration. From this point of view the overall
degradation, (b) kinetic study obtained using pseudo-first order model (Hold pollutant degradation would be controlled by diffusion and the mass
values: p1 = 4 bar, pH = 11 and T = 30 ◦ C). diffusion rate be linearly dependent on the concentration of pollutant in
the bulk liquid surrounding the film region.
This mechanism is correct only if the free radical concentration is low
Table 3 in the interfacial region since available pollutant molecules are suffi­
Kinetic rate constants at different initial concentration of cyanide.
cient to consume these free radicals. Thus, for low initial pollutant
[CN─]0 (mg L− 1) Degradation in 120 min (%) k x103 (min− 1) R2 concentration in the bulk the available free radicals are consumed by
100 51.3 6.49 0.984 available pollutant molecules with higher rates. However, for high
250 37.2 3.95 0.998 initial pollutant concentration the diffusion limitation is absent due to
400 29.9 3.27 0.987 saturation, yet the rates are lower because they are controlled by the free
550 28.5 3.10 0.981
radicals low concentration (Sivakumar et al., 2002).

(Malade and Deshannavar, 2018; Neppolian et al., 2002; Thanekar et al.,

3.3. Influence of pH of the solution
2020). Thanekar et al. (Thanekar et al., 2020) in the removal of nap­
roxen using an approach based on HC, reported the extent of degrada­
Solution pH may be one influential parameter to achieve an efficient
tion increased from 13.7% to 28.9% with a decrease in the initial
process of hydrodynamic cavitation because it may affect the chemical
concentration from 50 mg L− 1 to 10 mg L− 1. Malade et al. (Malade and
properties of the solution and the distribution of species. The effect of
Deshannavar, 2018) also reported a similar trend of higher degradation
solution pH on the performance of the cavitation process in the degra­
under corresponding conditions of lower pollutant initial concentration
dation of organic and inorganic compounds has already been studied,
of Reactive Red 120 of 10, 15, 20 and 25 mg L− 1.
concluding that there may be an optimal pH value for each type of
The HC/CN─ oxidation process is a multi-step heterogeneous reac­
contaminant to be treated (Choi et al., 2018; Dhanke et al., 2018; Tha­
tion. The CN─ reactant species starts its participation dissolved in the
nekar et al., 2018). In this sense, the effect of pH was analysed by car­
aqueous phase while the primary oxidant ●OH is generated by HC
rying out experiments in the range of 9.5 to 11, thus to avoid the
within the microbubbles. Thus, it is through the gas / aqueous interface
formation of highly toxic HCN (g) below pH 9.21 (pKa = 9.21 to 25 ◦ C)
that interphasial diffusional transport of reactants and products occur,
(Verhoeven et al., 1990). To this end, the optimized inlet pressure and
and at which the reaction between CN─ and ●OH may also occur
initial cyanide concentration values were fixed at 4 bar and 100 mg L− 1,
forming CNO─. In this scenario, the rate of generation of microbubbles,
respectively. The results are shown in Fig. 4a, where it is observed how
and consequent ●OH production may be taken as constant as it only
the degree of cyanide degradation increases with reducing pH. In 120
depends on external conditions such as HC reactor geometry, pressure
min the lowest extent of degradation, 51.3%, was observed at a pH value
and solution flowrate.
of 11. A degradation rate 1.4 times higher than the one obtained at pH
As seen in Fig. 3, the ln[CN─] versus time plots for any given value of
11 was achieved at pH 9.5. In this sense, Fig. 4a shows the free cyanide
CN─ initial concentration in the studied range show a fairly reasonable
degradation extent increases from 51.3 to 70% when pH is reduced from
linearity indicating a pseudo-first order dependence on CN─. However,
11 to 9.5, thus the relatively less basic medium is favourable for cyanide
as also seen by previous authors of HC treatment studies, when initial
ion degradation.
concentration is increased, the apparent rate constant (k) decreases. The
Fig. 4b shows the kinetic analysis of cyanide degradation with HC
results in Table 3 associated with the plots in Fig. 3b show that the re­
affected by solution pH, where it is observed it is a good fit for the
action’s apparent rate constant decreases from 6.49 × 10− 3 to 3.10 ×
pseudo-first order model. It is observed that the rate constant increases
10− 3 min− 1 when the initial cyanide concentration increases from 100
from 6.49 × 10− 3 to 10.41 × 10− 3 min− 1 as the pH decreases from 11 to

4
J.P. Montalvo Andia et al.
Fig. 4. Effect of solution pH (a) on the extent of cyanide degradation, (b) ki­
netic study obtained using pseudo-first order model (Hold values: p1 = 4 bar,
[CN─]0 = 100 mg L− 1 and T = 30 ◦ C).
9.5. This negative degradation trend with respect to pH has been iden­
tified in previous studies of CN─ oxidation in waters (Teixeira et al.,
2013). This may be due to the steric facility of the neutral HCN species
(pKa = 9.2) be more easily oxidized than the negatively-charged
dissociated form CN─. Similar results can be found in the literature.
Kitis et al. (Kitis et al., 2005) show the effect solution pH has on the
oxidation of cyanide with H2O2 and copper-impregnates pumice as
catalyst, they observed that the lower cyanide removal rate was at pH 11
compared to the rate at pH 8.
3.4. Effect of temperature
The effect of temperature on the rate of CN─ degradation was studied
at an inlet pressure of 4 bar, pH 9.5 and initial cyanide concentration of
100 mg L− 1. It can be seen in Fig. 5 that temperature has a relevant effect
on degradation rate and efficiency.
However, it is to note that, during hydrodynamic cavitation, tem­
perature may affect two opposite phenomena in the reaction kinetics.
The first is the common positive effect due to increasing temperature
increase the probability and rate of high energy inter-species collisions.
The second, according to previous authors, it is negative and is related to
the fact that an increase in temperature increases the vapor pressure of
the aqueous solution under treatment, which favours the excessive
Fig. 5. Effect of temperature (a) on the extent of cyanide degradation, (b) ki­
netic study obtained using pseudo-first order model (Hold values: p1 = 4 bar,
[CN─]0 = 100 mg L− 1 and pH = 9.5).
5
Minerals Engineering 171 (2021) 107119
generation of gaseous bubbles and leads to the formation of a cavitation
cloud, and consequently to a decrease of the collapse energy responsible
for the production of high local pressures and high temperatures that
occur in times of nanoseconds (Huang et al., 2015; Patil and Gogate,
2012).
In spite of these two opposite phenomena, it can be seen that for the
present work (Fig. 5a) increasing the temperature favoured the degra­
dation rate of cyanide. Wang and Zhang (Wang and Zhang, 2009) also
reported the increase in alachlor degradation with an increase in the
temperature of the solution, up to an optimum of 40 ◦ C, since at higher
temperatures (for example at 60 ◦ C) the presence of damped cavitation
effects exists.
Another reason why increasing temperature may not be entirely
favourable to degradation is the negative effect that high temperatures
have on the stability of H2O2. This compound is one of the oxidants
generated during cavitation which participates in the degradation of
contaminants due to its high oxidizing power.
The HC process activation parameters for cyanide degradation are
calculated using the Arrhenius equation and the Eyring equation (Eq.
(4)):
( ) ( #)
k KB ΔS# ΔH
ln = ln + − (4)
T h R RT
Where R is the universal gas constant (8.314 J mol− 1 K− 1), T is the
temperature (K), k is the reaction velocity constant, KB is the Boltzmann
constant (1.381 × 10− 23 J K− 1), h is the Planck constant (6.62 × 10− 34 J
s), ΔH# is the activation enthalpy (kJ mol− 1), and ΔS# is the activation
entropy (J mol− 1 K− 1).
Plotting “ln k” against “1/T”, according to the Arrhenius linear
equation, resulted in an activation energy value of 16.99 kJ mol− 1 for
cyanide degradation via hydrodynamic cavitation; as can be seen in
Fig. 6a. This value indicates a diffusion controlling step in the HC + CN─
reaction mechanism which may be due to slow diffusion of the reactants
●
OH or the CN─, or of a reaction product such as the CNO─ across the
liquid / gaseous microbubble interface.
Comparing this value to the ones obtained by Yeddou et al. (Yeddou
et al., 2010); 46.2 kJ mol− 1 and 82.7 kJ mol− 1 for the removal of cyanide
via H2O2 with and without the presence of activated carbon as a catalyst,
it is clearly seen that the Ea value obtained from experimental data is 2.7
times lower. It is also lower than the value of 32.2 kJ mol− 1 obtained by
Amaouche et al. (Amaouche et al., 2019) when evaluating the oxidation
of cyanide with H2O2, catalysed by the presence of CuO (1 g L− 1). The
lower value of Ea of the present work may be associated with the cata­
lytic effect provided by the hydrodynamic cavitation as it generates the
oxygen active species which act as a fast powerful oxidant for CN─ in
comparison with the silent – solely chemical reaction (Löning et al.,
2002).
Fig. 6b shows the application of the experimental data using the
Eyring linear equation to calculate ΔS# and ΔH#. The calculated value
for ΔH# was 14.45 kJ mol− 1, which indicates the degradation process is
endothermic in nature and that the reaction favours the formation of
CNO─ when temperature increases, as can be seen in Fig. 5 which shows
the effect of temperature.
For ΔS#, the obtained value was − 0.24 kJ mol− 1 K− 1 which indicates
a decrease in the degrees of freedom resulting in the formation of an
orderly activated complex. Normally, the activation entropy is negative
when the process implicates the system gets rearranged (Bolattin et al.,
2017; Rodrigues et al., 2017).
3.5. Combined effect of HC and hydrogen peroxide
The combined treatment of H2O2 with HC at different molar ratios
H2O2: CN─ of 1:1, 1.5:1, 3:1, 5:1 and 7:1, was studied to evaluate the
effect on speed and efficiency of cyanide degradation. The experiments
were carried at an initial concentration of 100 mg L− 1, inlet pressure of
J.P. Montalvo Andia et al. Minerals Engineering 171 (2021) 107119

1
Fig. 6. (a) Plot of linear Arrhenius equation (b) Plot of linear Eyring equation (Hold values: p1 = 4 bar, [CN─]0 = 100 mg L− and pH = 9.5).

4 bar, pH 9.5 and temperature of 30 ◦ C. The results obtained are shown

in Fig. 7, where it can be seen that when increasing the H2O2: CN─ molar
ratio from 1:1 to 5:1, the degree of degradation increases from
approximately 91% to 100%, reaching its maximum at molar ratio of 5:1
where cyanide is completely degraded in 60 min of operation. Beyond
this molar ratio, the degradation rate of cyanide is unaffected.
Furthermore, from Fig. 8 the pseudo-first order rate constants are ob­
tained for the combined process, observing that it also increases from
19.5 × 10− 3 (R2: 0.987) to 69.8 × 10− 3 (R2: 0.916) min− 1 for an increase
in the molar ratio of 1:1 to an maximum out of 5:1. This fact could be due
to the sweeping effect of excess hydrogen peroxide, which is known to
act as a hydroxyl radical scavenger through recombination and elimi­
nation pathways, decreasing the availability of ●OH radicals for the CN─
degradation reaction (Rajoriya et al., 2017).
From the results obtained, it is suggested that the combination HC +
H2O2 enhances the rate of ●OH generation, and as a consequence this
improves the oxidation rate of cyanide. This is observed to occur up to a
maximum molar ratio of 5:1; above that it remains constant (Thanekar
et al., 2018; Thanekar and Gogate, 2020) up to a maximum molar ratio Fig. 8. Comparison of cyanide degradation with HC, H2O2 only and HC + H2O2
out of 5:1, then it remains constant. In this sense, the oxidant H2O2 (Eho at different molar ratios (Hold values: p1 = 4 bar, [CN─]0 = 100 mg L− 1, pH =
= 1.78 V) can add to the effect of HC with additional formation of hy­ 9.5 and T = 30 ◦ C).
droxyl radicals (Baradaran and Sadeghi, 2019). It has been suggested
that taking advantage of the energy from the collapse of the cavitation of the synergic coefficient, calculated from Eq. (5). The addition of H2O2
effect will make the dissociation of the O-O bond from the H2O2 (213 kJ in a 5:1 molar ratio in the combined process, achieves a synergistic
mol− 1) faster than the O-H bond in the pyrolysis of H2O (418 kJ mol− 1), coefficient of 3.21, confirming that the combined HC + H2O2 technique
thus increasing the generation of ●OH (Gore et al., 2014). is better for its additive effect.
The efficiency of the hybrid process has been evaluated with the help
k(HC+H2 O2 )
Synergetic coefficient = (5)
kHC + kH2 O2

69.75x10− 3
= = 3.21
10.41x10− 3 + 11.30x10− 3

Other works report the benefits of the combination of hydrodynamic

Fig. 7. Cyanide degradation efficiency with HC, H2O2 only and HC + H2O2 at
different molar ratios (Hold values: p1 = 4 bar, [CN─]0 = 100 mg L− 1, pH = 9.5
and T = 30 ◦ C).
cavitation and hydrogen peroxide with a much greater degradation for
different types of pollutants (Aseev and Batoeva, 2014). Thanekar et al.
(Thanekar et al., 2018) investigated the application of the combined
effect of HC and H2O2 on the degradation of carbamazepine. The degree
of degradation was observed to increase from 31% to 58.3% when the
H2O2 charge increases in a molar ratio of 1:1 to 1:5. Thanekar et al.
(Thanekar et al., 2020) applied the hybrid HC and advanced oxidation
with H2O2 treatment strategy for Naproxen (NAP) degradation, using
different molar ratios of H2O2: NAP, verifying that the degree of
degradation increases from 34.4% to 80% when the molar ratio in­
creases from 50 to 1000. In addition, a maximum reduction of COD of
24% was observed, confirming the role of cavitation in improving the
degree of degradation.
Rajoriya et al. (Rajoriya et al., 2017) studied the degradation of a
cationic dye (Rhodamine 6G) using HC and H2O2, at different molar

6
J.P. Montalvo Andia et al. Minerals Engineering 171 (2021) 107119

ratios, observing that the rate constant of discoloration of Rh6G
increased from 3.0 × 10− 3 min− 1 using HC only to 21.6 × 10− 3 min− 1
when HC is combined with H2O2 at an optimal molar ratio of Rh6G:
H2O2 of 1:30. This is due to the added continuous dissociation of H2O2
into ●OH radicals by the effect of HC.
3.6. Calculating cavitation yield and process costs
Cavitation yield (Eq. (6)) expresses the amount of chemical change
achieved per unit of energy consumed, being that in the HC process, the
pump is the main component of energy consumption (Thanekar and
Gogate, 2019). A dissipated power per unit volume (determined as a
function of flow) of 5.16 W L− 1 was obtained for all studied processes
configurations. Table 4 provides the results of energy efficiency, specific
energy consumption, and total treatment cost for HC only and HC +
H2O2 processes. The cavitation yield of 1.88 × 10− 3 mg J− 1 obtained by
HC only, produces a degradation of 70% of cyanide in 120 min. It was
observed that the cavitation yield increases significantly to 2.69 × 10− 3
mg J− 1 when HC is combined with H2O2 in a minimum molar ratio of
1.5:1 to achieve a complete degradation of 100 mg L− 1 of cyanide in 120
min. Cavitation performance is observed to drastically increase to 5.38
× 10− 3 mg J− 1 when the molar ratio is increased to a value of 5:1. It is
noteworthy here that the cavitation performance is maximum in a 5:1
ratio, contrary to its initial degradation kinetic rate, since there would be
a sufficient amount of H2O2 to achieve cyanide degradation in the
shortest time. Therefore, the combination of HC + H2O2 in a process is
an energy efficient technique for cyanide degradation, compared to
applying the processes separately. Thanekar et al. (Thanekar et al.,
2018), obtained a cavitation yield of 1.57 x 10− 4 mg J− 1 for the com­
plete degradation of 10 mg L− 1 carbamazepine (CBZ) using HC + H2O2
+ O3 with an optimal CBZ: H2O2 molar ratio of 1:5 and a ratio flow rate
of 400 mg O3 h− 1, under optimized operational conditions. Kumar et al.
(Kumar et al., 2017) investigated the effectiveness of HC in the degra­
dation of methylene blue (MB) dye. They found that HC combined with
H2O2 at an optimal molar ratio of MB: H2O2 of 1:20 has the highest
effectiveness (99.64% discoloration in 60 min) with a cavitation per­
formance of 5.99 x 10− 6 mg J− 1 for mineralization of organic carbon in
the aqueous solution.
Extent of degradation
Cavitational yield = (6)
Power dissipation
The energy cost has been found to decrease from 0.00078 to 0.00021
USD L− 1 of treated effluent when molar ratio H2O2: CN─ increases from
1: 1 to 7: 1. Consequently, the costs of the reagent used (H2O2) are
increased from 0.0012 to 0.0084 USD L− 1 of treated effluent, obtaining
that at a minimum H2O2: CN─ ratio of 1.5:1, a balance is reached be­
tween the energy cost and the cost of the added peroxide, giving a total
treatment value of 0.00073 USD L− 1 in 120 min of operation, for the
removal of 100% of free cyanide.
Jawale and Gogate (Jawale and Gogate, 2019) reported a cavitation
yield of 0.9725 x 10− 5 mg J− 1 using HC, achieving a degree of degra­
dation of 52.8% of thiocyanate from an initial concentration of 20 mg
L− 1, at a cost of 0.018 USD L− 1. This value exceeds that obtained in the
present study, indicating that the combined HC and H2O2 approach is an
economically viable process.
The specific energy consumption was calculated using the following
equation:
P×t
Es = (7)
[ΔX] × V
Where, Es: is the specific energy consumption, P: electrical power sup­
plied (kW), t: operating time (h), [ΔX]:
amount of CN─ degraded (kg) and V: volume of water treated (L).
The results indicate the hybrid HC + H2O2 process (1.5:1 M ratio)
presents a specific energy consumption of 103.26 kWh kg− 1; a lower
value compared to the 147.52 kWh kg− 1 obtained for HC as a stand-
alone process. Comparing these results with other advanced oxidation
CN─ degradation processes; Mudliar et al. (Mudliar et al., 2009) re­
ported a specific energy consumption of 168 kWh kg− 1 for the combi­
nation of UV-based advanced oxidation with H2O2 to treat a synthetic
solution of sodium cyanide at an initial concentration of 100 mg L− 1,
and Perez et al. (Pérez et al., 2017) obtained a specific energy con­
sumption of 261.70 kWh kg− 1 for an electrolytic cyanide degradation
process (which initially contained 100 mg L− 1 CN─) using a Ti-RuO2
anode in a filter-press electrolyser, reaching a degradation efficiency of
94% in 480 min. These values exceed the ones obtained in the present
study, which tells us the combined HC + H2O2 approach is an
economically viable process for cyanide removal compared to other
technologies.
With respect to a future interest in scaling up the present bench-scale
batch process to a continuous-flow staged operation, it would be
necessary to evaluate a suitable scale configuration, optimal scaling
parameters, ratio of inlet pressure and outlet pressure that influence the
process efficiency to expand the HC plant to an industrial scale (Wang
et al., 2021).
In the present specific case of the combined HC + H2O2 process, the
batch reaction mode had an added complexity compared to a simple
batch stirred tank reactor. It consisted of the addition of an initial shot of
H2O2 into a solution containing a given initial concentration of target
pollutant CN─ and a constant distribution of microbubbles generated by
HC which provided a continuous supply of radical species ●OH due to
decomposition of H2O in the microbubbles, in addition to the supply of
●
OH due to H2O2 decomposition. Given the specificity and complexity
of the present HC + H2O2 system, the reader may be referred to the
works of Sarvothaman et al. (Sarvothaman et al., 2020, 2018) for
translation of data from batch experiments to design of continuous
cavitation-based wastewater treatments.

Table 4
1.
Comparison of different combined processes in terms of cavitation performance, specific energy consumption and total cost. Initial [CN─] = 100 mg L−
a b
System H2O2: Kinetic constant Degradation Cavitational Yield Required Energy Energy costs H2O2 costs Total cost of
CN─ (10− 3 min− 1) yield (%) x103 (mg J− 1) (kWh) (USD L− 1) (USD L− 1) treatment (USD L− 1)

HC only – 10.4 70 1.88 0.0148 0.00078 – 0.00078

HC + 1: 1 19.5 91 2.45 0.0113 0.00060 0.00012 0.00072
H2O2
HC + 1.5: 1 24.7 100 2.69 0.0103 0.00055 0.00018 0.00073
H2O2
HC + 3: 1 29.56 100 3.58 0.0077 0.00041 0.00036 0.00077
H2O2
HC + 5: 1 69.8 100 5.38 0.0052 0.00027 0.00060 0.00087
H2O2
HC + 7: 1 47.34 100 7.17 0.0039 0.00021 0.00084 0.00105
H2O2
a
Electric energy cost: 0.053 USD kWh− 1.
b
Hydrogen peroxide cost: 0.90 USD kg− 1 (H2O2 100% active substance).

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J.P. Montalvo Andia et al. Minerals Engineering 171 (2021) 107119

A recent comprehensive review covering the fundamental and CNO─ product.

operational aspects of scaling HC treatments was published by Wang
et al. (Wang et al., 2021).
4. Conclusions
The present investigation on the use of hydrodynamic cavitation
combined with H2O2 as an alternative to treat cyanide-containing syn­
thetic effluents with initial concentration of free cyanide in the range
100 – 550 mg L− 1 revealed that the extent of CN─ degradation in 120
min with simple hydrocavitation was limited to 70 %, whereas the
combination of HC + H2O2 resulted in almost complete degradation
(99.9 %) within the same time using a molar ratio of H2O2:CN─ = 1.5:1.
The influence of the parameters: inlet pressure; H2O2:CN─ ratio; pH
and temperature have been evaluated, and the optimal values found
were: inlet pressure 4 bar; H2O2:CN─ ratio 1.5; and pH 9.5, for a given
temperature in the studied range 20 to 50 ◦ C.
In each kinetic run the plot of ln [CN─] vs time was reasonably linear
2
(R > 95%) in accordance with a possible pseudo first-order behaviour
with respect to CN─. However, the negative effect of initial [CN─] on the
reaction rate indicated that a large concentration of CN─ at the start of
the reaction hinders the reaction possibly by blocking the interface for
diffusion of reacting / product species or the sites where the actual re­
action between CN─ and the generated ●OH occurred producing the
The effect of temperature on the reaction rate gave an apparent
activation energy value of 17.0 kJ mol− 1 indicating that the overall
reaction is controlled by a diffusional step.
The operating cost for 99.9% removal of cyanide with the hybrid
process, considering H2O2 consumption and power requirement was
0.00073 USD L− 1, a competitive value with a process using H2O2 only at
a H2O2:CN─ molar ratio of 6:1.
CRediT authorship contribution statement
Javier Montalvo Andia: Conceptualization, Methodology, Writing
– original draft, Project administration. Alberth Ticona: Writing –
original draft, Methodology, Investigation, Validation. Jocelyn Ill­
achura: Methodology, Investigation, Visualization. Lizandra Lopez:
Writing – original draft, Investigation, Resources. Miguel Cardenas:
Writing – original draft, Resources, Formal analysis. Luiz Alberto Cesar
Teixeira: Writing – review & editing, Supervision, Resources.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.

Appendix A

Model calculation of Cavitation Number at an optimum 4 bar inlet pressure:

Inlet pressure (p1) = 4 bar = 4 × 105 Pa
Outlet pressure (p2) = 1.2 bar = 1.2 x 105 Pa
Vapor pressure of water at operating temperature (pv) = 4241.14 Pa
Volumetric flow rate at optimum pressure of 4 bar (Q) = 664 L h− 1 = 1.844 × 10− 4
m3 s− 1

Dimension of the throat of the venturi according to Table 1:

W = 6.0 mm, H = 1.9 mm, L = 1.9 mm
Throat area (A0) = 1.14x10− 5 m2
Velocity at the throat:
Q 1.844x10− 4 1
v= = = 16.18ms−
A0 1.14x10− 5
Cavitation number is calculated according to Eq. (3):
p2 − pv 120000 − 4241.14
Cv = 1
=
2
ρv 2 0.5x1000x(16.18)2
=0.88

Appendix B

Model calculation of Cavitational yield at optimal conditions of operation:

Pressure drop across the slit venturi (Δp) = 2.8 x105 Pa
Power dissipated into the system (W)
= Pressure drop across the venturi (Pa) × volumetric flow rate (m3s− 1)
= (2.8 x105) × (1.844 × 10− 4)
= 51.632 W
Power dissipated per unit volume (W L− 1) = 51.632
10 = 5.163 W L− 1
− 1
Initial CN concentration = 100 mg L
─
1
Amount of CN─ degraded using only HC in 120 min of reaction = 70 mg L− (70% of degradation)
( )
70
Cavitational yield =
5.1632x120x60
Cavitational yield = 1.88x10− 3 mg J− 1
Model calculation of Cost of treatment:
Energy required for degradation of cyanide per unit volume treated
100 − 7
= 1.88x10− 3 x2.78x10 = 0.0148 kWh L− 1
Electric energy cost = 0.053 USD kWh− 1

8
J.P. Montalvo Andia et al. Minerals Engineering 171 (2021) 107119

Cost of treatment = 0.00078 USD L− 1

Similarly, the energy efficiencies for the other processes were calculated and compared

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